Method of improving steam flood conformance with steam flooding agents without a non-condensable gas

ABSTRACT

The disclosed invention is a group of novel steam foaming agents for injection with steam to decrease permeability in steam sept zones. They are effective without the coinjection on a non-condensable gas. The foaming agents have the general formula: RO(R&#39;O)nR&#39;&#39;SO3M where R is an alkyl radical, branched or linear, having from about 15 to about 21 carbon atoms in the alkyl chain, R&#39; is ethyl or propyl, n has an average value of about 2 to about 5, R&#39;&#39; is ethyl, propyl, hydroxypropyl or butyl and M is an alkali metal or ammonium ion.

BACKGROUND OF THE INVENTION

This application is a continuation-in-part application of U.S. patent application Ser. No. 06/576,692, filed Feb. 3, 1984, now abandoned.

This application is related to concurrently filed, copending U.S. patent applications Ser. No. 638,919, filed Aug. 8, 1984, and Ser. No. 638,920, filed Aug. 8, 1984, both of which are incorporated herein by reference. The present invention relates to a steam foaming agent which when injected with steam will significantly improve vertical conformance without the use of a non-condensable gas.

When an oil reservoir is subjected to steam injection, steam tends to move up in the formation, whereas condensate and oil tends to move down due to the density difference between the fluids. Gradually, a steam override condition develops, in which the injected steam sweeps the upper portion of the formation but leaves the lower portion untouched. Injected steam will tend to follow the path of least resistance from the injection well to a production well. Thus, areas of high permeability will receive more and more of the injected steam which further raises the permeability of such areas. This phenomenon exists to an even larger degree with low injections rates and thick formations. The steam override problem worsens at greater radial distances from the injection well because steam flux decreases with increasing steam zone radius.

Although residual oil saturation in the steam swept region can be as low as 10%, the average residual oil saturation in the formation remains much higher due to poor vertical conformance. Thus it is because of the creation of steam override zones that vertical conformance in steam floods is usually poor.

It has long been the concern of the oil industry to improve the vertical conformance of a steam flood by reducing the permeability of the steam swept zone by various means. The injection of numerous chemicals such as foams, foaming solutions, gelling solutions or plugging or precipitating solutions have been tried. Because of the danger of damaging the reservoir, it is considered important to have a non-permanent means of lowering permeability in the steam override zones. For this reason, certain plugging agents are not deemed acceptable. In order to successfully divert steam and improve vertical conformance, the injected chemical should be (1) stable at high steam temperatures of about 300° to about 600° F., (2) effective in reducing permeability in steam swept zones, (3) non-damaging to the oil reservoir and (4) economical.

The literature is replete with references to various foaming agents which are employed to lower permeability in steam swept zones. The foaming agents of the prior art require the injection of a non-condensable gas to generate the foam in conjunction with the injection of steam and the foaming agent. U.S. Pat. Nos. 3,366,175 and 3,376,924 disclose the injection of a steam foam in a hydrocarbon reservoir at the interface between the hydrocarbons and the gas cap to aid in recovery. U.S. Pat. Nos. 3,410,344 and 3,994,345 disclose the use of a steam foaming agent selected from the generic groups of polyethoxyalkanols and alkylaryl sulfonates to reduce permeability in steam channels. The use of similar surfactants such as sodium lauryl sulfoacetate and alkyl polyethylene oxide sulfate are disclosed as foaming agents in carbon dioxide foams in U.S. Pat. Nos. 4,088,190 and 4,113,011, respectively. U.S. Pat. No. 4,018,278 discloses the use of sulfonated, ethoxylated alcohols or alkylphenols in surfactant flooding solutions without the use of steam.

Several trademarked foaming agents have been field tested by petroleum companies in steam floods. These include such trademarked chemicals as Stepanflo 30 sold by Stepan Chemical Co., Suntech IV sold by Sun Oil, Thermophoam BWD sold by Farbest Co. and COR-180 sold by Chemical Oil Recovery Co. U.S. Pat. No. 4,086,964 discloses the use of lignin sulfonates for a foaming agent and 4,393,937 discloses the use of alpha olefin sulfonates as a steam foaming agent. See also United Kingdom Pat. No. 2,095,309 for a disclosure of alpha olefin sulfonate foaming agents.

Disclosures of laboratory and field tests of Stepanflo are contained in SPE Paper No. 10774 entitled "The Laboratory Development and Field Testing of Steam/Noncondensible Gas Foams for Mobility Control in Heavy Oil Recovery" by Richard E. Dilgren et al. presented at the 1982 California Regional Meeting of the SPE held in San Francisco Mar. 25-26, 1982 and the Journal of Petroleum Technology, July 1982, page 1535 et seq. The same Journal of Petroleum Technology also discusses tests conducted on Thermophoam BWD. Additional information on tests of Thermophoam BWD are also disclosed in Department of Energy Publications DOE/SF-10761-1, -2 and -3.

Tests of the COR-180 foaming agent of Chemical Oil Recovery Co. are disclosed in SPE Paper No. 11806 entitled "Improvement in Sweep Efficiencies in Thermal Oil-Recovery Projects Through The Application of In-Situ Foams" by R. L. Eson, presented at the International Symposium on Oil Field and Geothermal Chemistry in Denver, June 1-3, 1983 and Department of Energy Reports Nos. DOE/SF/10762-1, -2 and -3.

SUMMARY OF THE INVENTION

The present invention pertains to novel steam foaming agents for injection with steam to decrease permeability in steam swept zones and ultimately, increase oil recovery with steam flooding. These novel foaming agents are effective without the coinjection of a non-condensable gas. The steam injected with the foaming agent provides the gas to create the foam.

The novel foaming agents have the general formula:

    RO(R'O).sub.n R"SO.sub.3.sup.- M.sup.+,

where R is an alkyl radical, branched or linear, having from about 15 to about 21 carbon atoms in the alkyl chain, R' is ethyl or propyl, n has an average value of about 2 to about 5, R" is ethyl, propyl, hydroxypropyl or butyl and M is an alkali metal or ammonium ion.

DETAILED DESCRIPTION

The steam foaming agents for the present invention are highly effective in reducing permeability of steam swept zones. These novel foaming agents have an affinity for formation areas of high permeability and low oil saturation. When set up in such areas, they substantially reduce the permeability of the steam swept zones, forcing steam into other, unswept areas of the formation.

The novel steam foaming agents of the present invention are represented by the general chemical formula:

    RO(R'O).sub.n R"SO.sub.3.sup.- M.sup.+,

where R is an alkyl radical, branched or linear, having from about 15 to about 21 carbon atoms in the alkyl chain, R' is ethyl or propyl, preferably ethyl, n has an average value of about 2 to about 5, preferably about 3 to about 4, R" is ethyl, propyl, hydroxypropyl or butyl and M is an alkali metal or ammonium cation. The preferred alkali metal ions are sodium, lithium and potassium. It should be noted that n is an average value and that the invention compounds will normally have varying degrees of ethoxylation.

These novel foaming agents are stable at the high temperatures encountered in steam floods (300° to 600° F.). They are not permanent and do not damage the reservoir. And most importantly, these foaming agents may be employed without the use of a non-condensable gas. As a result, these foams offer substantial economic advantages over other steam foaming agents which require the injection of significant quantities of a non-condensable gas.

The three most preferred foaming agents are three alcohols herein labeled Agents 2, 3 and 4, which correspond to the example numbers. Their cost of manufacture compares very favorably with the cost of existing foaming agents which additionally require the use of expensive quantities of a non-condensable gas. Although the preferred agents illustrated below have linear saturated alkyl radicals for the R substituent, it should be noted that the saturated alkyl radical may also be branched. The chemical formulas of the most preferred foaming agents are: ##STR1##

The mixture of steam and foaming agent can bring about a substantial reduction in permeability when injected into the high permeability areas of the formation at almost any time. Vertical conformance will be significantly improved whether the steam foaming agent is injected into the formation at the very beginning of steam injection, before steam breakthrough at the production well or after steam breakthrough. The most preferred injection times occur shortly after steam injection has begun and a short time before steam breakthrough will occur at the production wells. In the first instance, the injection of the steam foaming agent near the beginning of steam injection will help prevent narrow steam channels from being formed and extended through to the production wells. The injection of the foaming agent prior to steam breakthrough will postpone the time of steam breakthrough and spread the steam over a wider area near the production wells.

The invention foaming agents will also work quite well if steam breakthrough occurred in the past and low oil saturation steam override zones exist. But in such a situation, the foaming agent must be injected in larger concentrations and greater quantities to reduce permeability in a frequently swept area. Generally, the mixture of steam and foaming agent must be injected into the reservoir at a higher pressure than the previous injection of steam so that the foam will move a sufficient distance into the high permeability areas. However, the injection pressure must be less than the reservoir fracturing pressure or damage to the formation will occur.

The foaming agent and steam should be injected in a mixture such that the foaming agent comprises about 0.01% to about 5%, preferably about 0.02% to about 1.5% by weight of the steam. It is contemplated that the injected steam range from about 20% to about 90% quality. A higher concentration of foaming agent is generally necessary if the region has been swept by steam for a considerable time. But individual tests should be run to tailor the concentration of the foaming agent in steam as the increased effectiveness of the foaming agent per increased concentration of foaming agent quickly reaches a point of diminishing returns. Furthermore, other surfactants may also be included in the steam and foaming agent mixture to increase oil recovery providing they do not substantially inhibit the foam.

No chemical or physical deterioration has been detected in the foaming agents used in the formation at steam injection temperatures. Additionally, no problems have been encountered with thermal or hydrolytic stability of the agents. The foams tested have continued to be effective up to three days but since the foaming agent will be eventually produced, it is generally necessary to continue injecting foam into the high permeability areas. Cooling problems also fail to affect foam stability. This is because the foam will go preferentially into the high permeability areas of the steam override which are very hot. The cool areas of the formation are those areas of low permeability which the foam will avoid.

The following examples will further illustrate the novel steam foaming agents of the present invention. These examples are given by way of illustration and not as limitations on the scope of the invention. Thus, it should be understood that the composition and concentration of the foaming agents may be varied to achieve similar results within the scope of the invention.

EXAMPLES 1-11

Multiple runs were made in a special foam testing apparatus to determine the effectiveness of the foaming agents of the present invention and several well known steam foaming agents when injected with steam in the absence of a non-condensable gas. A 90 cm linear cell with a diameter of 3.4 cm was packed with sand, oil and water to a porosity of 0.4 and an oil saturation of 0.2. The sand pack was steam flooded at 4 ml per minute of cold water equivalent until no more oil was produced. The pressure drop across the cell length with the steam injection only was measured and determined to be approximately 10 psig in Example 1. A high concentration of 6% active foaming agent (corresponding to about a 1% in situ concentration in the aqueous phase in the cell) was then injected with steam at approximately 0.5 ml per minute. The pressure drop was measured continuously and recorded when it stabilized.

Examples 2, 3 and 4 show pressure drops across the cell of some 11 to 18 times the pressure drop experienced with injection of steam alone. These three foaming agents, Agents 2, 3 and 4, were considered very effective. Examples 5 and 6 were performed with foaming agents that are related structurally to the foaming agents of the present invention but do not fall within the scope of the invention. These agents of Examples 5 and 6 as well as the well known steam foaming agents of Examples 7-11 were completely ineffective when injected with steam without the presence of a non-condensable gas.

                  TABLE I                                                          ______________________________________                                                                 Pressure Drop                                          Ex.      Foaming Agent  Across Cell (psig)                                     ______________________________________                                         1        Steam Only      10                                                    2        Agent 2        120                                                    3        Agent 3        185                                                    4        Agent 4        110                                                    5        Agent 5        10                                                     6        Agent 6        10                                                     7        Stepanflo 30   10                                                     8        Stepanflo 1390 10                                                     9        Thermophoam BWD                                                                               10                                                     10       Bioterge AS-40 10                                                     11       Suntech IV     10                                                     ______________________________________                                          Agent 5  a compound with the formula                                           ##STR2##                                                                       Agent 6  a compound having the same structure as Agent 3 except that the       alkyl radical R contains 12-14 carbon atoms.                                   Stepanflo 30 and 1390  trademarked alpha olefin sulfonates sold by Stepan      Chemical Co.                                                                   Thermophoam BWD  a trademarked alpha olefin sulfonate sold by Farbest Co.      Bioterge AS40  a trademarked alpha olefin sulfonate sold by Stepan             Chemical Co.                                                                   Suntech IV  a trademarked sulfonate sold by Sun Oil Co.                  

EXAMPLES 12-14

Tests were also conducted in a dual pack apparatus prepared as per Examples 1-11, wherein two 90 cm linear sandpacks were connected in parallel so that the mixture of steam and foaming agent would have an equal opportunity to travel into and through each of the two sandpacks. One of the cells was a high oil saturation pack having an oil saturation of approximately 35% and the second cell was a low oil saturation sandpack having an oil saturation of about 20%.

When steam was injected, the vast majority of steam passed through the low oil saturation pack having higher permeability. But as indicated in Table II, when the steam was injected with Agents 2 and 3 at a concentration of about 6% (corresponding to about a 1% in situ concentration in the aqueous phase in the cell), most of the injected steam went through the low permeability, high oil saturation sandpack.

                  TABLE II                                                         ______________________________________                                                    % Of Injected Steam Through Each Cell                               Ex.              Low Oil Saturation                                                                           High Oil Saturation                             ______________________________________                                         12   Steam       71.7%         28.3%                                                Injection Only                                                            13   Steam and   41.5%         58.5%                                                Agent 2                                                                   14   Steam and   15.4%         84.6%                                                Agent 3                                                                   ______________________________________                                    

Many other variations and modifications may be in the concepts described above by those skilled in the art without departing from the concepts of the present invention. Accordingly, it should be clearly understood that the concepts disclosed in the description are illustrative only and are not intended as limitations on the scope of the invention. 

What is claimed is:
 1. A process for recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises:injecting steam into an injection well; injecting into the injection well a mixture of steam and about 0.01% to about 5% by weight of a foaming agent based upon the weight of the steam in the injected mixture, said foaming agent represented by the formula,

    RO(R'O).sub.n R"SO.sub.3.sup.- M.sup.+,

where R is an alkyl radical, branched or linear, having from about 15 to about 21 carbon atoms in the alkyl chain, R' is ethyl or propyl, n has an average value of about 2 to about 5, R" is ethyl, propyl, hydroxypropyl or butyl, and M⁺ is an alkali metal or ammonium ion; injecting steam into said injection well; and recovering hydrocarbons and other fluids at a production well.
 2. The process of claim 1 for recovering hydrocarbons, wherein said mixture is injected into a steam override zone.
 3. The process of claim 1 for recovering hydrocarbons wherein R is an alkyl radical having about 16 to about 18 carbon atoms, R' is ethyl, n has an average value of about 3 to about 4, R" is propyl and M⁺ is sodium.
 4. The process of claim 1 for recovering hydrocarbons, wherein R is an alkyl radical having about 16 to about 20 carbon atoms, R' is ethyl, n has an average value of about 3, R" is propyl and M⁺ is sodium.
 5. The process of claim 1 for recovering hydrocarbons, wherein the concentration of said foaming agent in steam is increased as the steam injection rate is increased.
 6. The process of claim 1 for recovering hydrocarbons, wherein said mixture is injected into an injection well near the beginning of steam injection.
 7. The process of claim 1 for recovering hydrocarbons, wherein said mixture is injected into an injection well immediately prior to steam breakthrough at a production well.
 8. The process of claim 1 for recovering hydrocarbons, wherein said mixture is injected into an injection well after steam breakthrough at a production well.
 9. A process for recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises:injecting into an injection well a mixture of steam and about 0.01% to about 5% by weight of a foaming agent based upon the weight of the steam in the injected mixture, said foaming agent represented by the formula,

    RO(R'O).sub.n R"SO.sub.3.sup.- M.sup.+,

where R is an alkyl radical, branched or linear, having from about 15 to about 21 carbon atoms in the alkyl chain, R' is ethyl or propyl, n has an average value of about 2 to about 5, R" is ethyl, propyl, hydroxypropyl or butyl, and M⁺ is an alkali metal or ammonium ion; injecting steam into said injection well; and recovering hydrocarbons and other fluids at a production well.
 10. A process for recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises:injecting into an injection well a mixture of steam and about 0.02% to about 1.5% by weight of a foaming agent based upon the weight of steam in the injected mixture, said foaming agent represented by the formula, ##STR3## injecting steam into said injection well; and recovering hydrocarbons and other fluids at a production well. 